US9085722B2 - Acryloylmorpholine polymer and use thereof and filtrate reducer for drilling fluid - Google Patents
Acryloylmorpholine polymer and use thereof and filtrate reducer for drilling fluid Download PDFInfo
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- US9085722B2 US9085722B2 US14/031,115 US201314031115A US9085722B2 US 9085722 B2 US9085722 B2 US 9085722B2 US 201314031115 A US201314031115 A US 201314031115A US 9085722 B2 US9085722 B2 US 9085722B2
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- 0 *C.[1*]C(C)C([2*])(C)C(=O)N1CCOCC1.[4*]C(C)C([5*])(C)C(=C)NC([6*])([7*])CS(=O)(=O)OC.[4*]C(C)C([5*])(C)C(=O)C([10*]CC(=O)C([9*])(C)C([8*])C)C([6*])([7*])CS(=O)(=O)OC.[8*]C(C)C([9*])(C)C(=C)C[10*]O Chemical compound *C.[1*]C(C)C([2*])(C)C(=O)N1CCOCC1.[4*]C(C)C([5*])(C)C(=C)NC([6*])([7*])CS(=O)(=O)OC.[4*]C(C)C([5*])(C)C(=O)C([10*]CC(=O)C([9*])(C)C([8*])C)C([6*])([7*])CS(=O)(=O)OC.[8*]C(C)C([9*])(C)C(=C)C[10*]O 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N CCC(C)C Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- C08F2220/585—
Definitions
- the present invention relates to an acryloylmorpholine polymer, an use of the acryloylmorpholine polymer as a filtrate reducer for drilling fluid, and a filtrate reducer for drilling fluid.
- oil-based drilling fluid systems are used in 60-70% horizontal shale gas wells in foreign countries; in addition, oil-based drilling fluids are used in most horizontal shale gas wells finished recently in China.
- water-based drilling fluids are the best choice, because oil-based drilling fluids have high cost and environmental pollution problems.
- the active shale rocks may have water loss or dehydration phenomenon when they are exposed to water-based drilling fluids with high salinity (e.g., 35% CaCl 2 water solution).
- it is urgent task to develop a filtrate reducer that has outstanding filtrate reduction performance and viscosity increasing effect, to meet the requirements of horizontal well drilling for shale gas.
- the object of the present invention is to provide an acryloylmorpholine polymer which has outstanding filtrate reduction performance and viscosity increasing effect, use of the acryloylmorpholine polymer as a filtrate reducer for drilling fluid, and a filtrate reducer for drilling fluid.
- the present invention provides an acryloylmorpholine polymer, comprising structural units expressed by formula (1), structural units expressed by formula (2), and structural units expressed by formula (3), wherein, at least a part of the structural units expressed by formula (2) are bonded with at least a part of the structural units expressed by formula (3) into cross-linked structural units expressed by formula (4); on the basis of 1 mol structural units expressed by formula (1), the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 0.5-10 mol, and the total content of the structural units expressed by formula (3) and the cross-linked structural units expressed by formula (4) is 0.01-0.05 mol;
- R 1 -R 9 are H or C 1 -C 3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R 10 is C 1 -C 5 linear or branched alkylidene.
- the present invention further provides a filtrate reducer for drilling fluid, which is prepared with a method that comprises the following steps:
- step (II) controlling the product obtained in step (I) to have cross-linking reaction under cross-linking reaction conditions
- R 1 -R 9 are H or C 1 -C 3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R 10 is C 1 -C 5 linear or branched alkylidene.
- the present invention further provides an use of the acryloylmorpholine polymer as a filtrate reducer for drilling fluid.
- the present invention has the following beneficial effects: the hydrolysis-resistant monomer A that has large pendant group and the monomer B that contains sulfonic (sulfonate) groups are controlled to have copolymerization reaction in existence of the cross-linked monomer C, so that the obtained filtrate reducer for drilling fluid has appropriate degree of cross-linking, and thereby has not only outstanding filtrate reduction performance but also good viscosity increasing effect under high temperature, high salinity, and high calcium content conditions, i.e., the obtained filtrate reducer for drilling fluid has high temperature resistance and salt resistance performance.
- the filter loss can be reduced to equal to or less than 14.0 mL, the apparent viscosity can be increased to equal to or above 11.5 mPa ⁇ s, and the plastic viscosity can be increased to equal to or above 8.5 mPa ⁇ s;
- the filter loss can be reduced to equal to or less than 15.5 mL, the apparent viscosity can be increased to equal to or above 10.5 mPa ⁇ s, and the plastic viscosity can be increased to equal to or above 5 mPa ⁇ s; for a saturated brine base mud that contains the filtrate reducer for drilling fluid in the present invention, after aging for 16 h at 220° C
- the filtrate reducer for drilling fluid is prepared by controlling the reactants to have polymerization reaction quickly in an aqueous solvent and then controlling the polymerization product to have cross-linking reaction.
- the preparation process is easy to control, the operation is simple, the product quality is stable, and the production and drying process consume low energy, and the preparation process has no environmental pollution.
- the acryloylmorpholine polymer provided in the present invention comprises structural units expressed by formula (1), structural units expressed by formula (2), and structural units expressed by formula (3), wherein, at least a part of the structural units expressed by formula (2) are bonded with at least a part of the structural units expressed by formula (3) into cross-linked structural units expressed by formula (4); on the basis of 1 mol structural units expressed by formula (1), the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 0.5-10 mol, preferably 0.7-9.17 mol, and the total content of the structural units expressed by formula (3) and the cross-linked structural units expressed by formula (4) is 0.01-0.05 mol, preferably 0.011-0.047 mol;
- R 1 -R 9 are H or C 1 -C 3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R 10 is C 1 -C 5 linear or branched alkylidene.
- the C 1 -C 3 linear or branched alkyl can be methyl, ethyl, n-propyl, or isopropyl.
- the C 1 -C 5 linear or branched alkylidene can be methylene, ethylidene, n-propylidene, iso-propylidene, n-butylidene, iso-butylidene, n-pentylidene, or iso-pentylidene.
- the alkali metal element can be one or more selected from the group consisting of Li, Na, and K.
- M is H, K, or Na. M can be the same or different among different structural units of the same polymer.
- R 1 -R 3 are H; in that case, the monomer corresponding to the structural unit is N-acryloylmorpholine.
- R 4 and R 5 are H, R 6 and R 7 are methyl, y is 1, and M is Na; in that case, the monomer corresponding to the structural unit is 2-acrylamide-2-methyl propane sulfonic acid sodium.
- R 8 and R 9 are H, X is NH, and R 10 is methylene; in that case, the monomer corresponding to the structural unit is N-methylol acrylamide; or,
- R 8 and R 9 are H, X is O, and R 10 is ethylidene; in that case, the monomer corresponding to the structural unit is hydroxyl-ethyl acrylate; or,
- R 8 is H, R 9 is methyl, X is O, and R 10 is ethylidene; in that case, the monomer corresponding to the structural unit is hydroxyl-ethyl methacrylate; or,
- R 8 and R 9 are H, X is O, and R 10 is
- the monomer corresponding to the structural unit is hydroxy-propyl acrylate.
- the apparent viscosity of the acryloylmorpholine polymer there is no specific restriction to the apparent viscosity of the acryloylmorpholine polymer; preferably, the apparent viscosity of 1 wt. % water solution of acryloylmorpholine polymer is 30-55 mPa ⁇ s.
- the apparent viscosity is measured with a Fan-35 rotary viscosimeter at 25° C.
- the filtrate reducer for drilling fluid provided in the present invention is prepared with a method that comprises the following steps:
- step (II) controlling the product obtained in step (I) to have cross-linking reaction under cross-linking reaction conditions
- R 1 -R 9 are H or C 1 -C 3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R 10 is C 1 -C 5 linear or branched alkylidene.
- the aqueous solvent can be any existing solvent with water that can be used as a reaction medium; for example, it can be water or mixture of water and any other solvent, preferably is water.
- the dosage of the aqueous solvent can be 50-150 parts by weight.
- the monomer A is N-acryloylmorpholine.
- the monomer B is 2-acrylamide-2-methyl propane sulfonic acid sodium.
- the monomer B is 2-acrylamide-2-methyl propane sulfonic acid sodium
- it can be bought commercially or prepared with the following method: controlling 2-acrylamide-2-methyl propane sulfonic acid and sodium carbonate or sodium hydroxide to have neutralization reaction in water solution at a temperature not higher than 15° C., and filtering off the impurities after the reaction.
- the preparation process of 2-acrylamide-2-methyl propane sulfonic acid sodium is a purification process of 2-acrylamido-2-methyl propane sulfonic acid.
- the cross-linked monomer C is one or more selected from the group consisting of N-ethoxyl acrylamide, N-methylol acrylamide, hydroxy-methyl acrylate, hydroxy-methyl methacrylate, hydroxy-ethyl acrylate, hydroxy-ethyl methacrylate, hydroxy-propyl methacrylate, and hydroxy-propyl acrylate; especially preferably, the cross-linked monomer C is one or more selected from the group consisting of N-methylol acrylamide, hydroxy-ethyl acrylate, hydroxy-ethyl methacrylate, and hydroxy-propyl acrylate.
- the monomer B is used preferably in a form of 40-60 wt. % water solution.
- the above-mentioned substances can be added together into the aqueous solvent and agitated to homogeneous state; particularly preferably, homogeneously mixing a water solution of monomer B with water first; then, adding monomer A and cross-linked monomer C and agitating to homogeneous state; next, adjusting the pH of the obtained mixture to 6-9, and then adding the initiator.
- the dosage of water includes the dosage of water in the water solution of the monomer B.
- the method for adjusting the pH of the mixture is well known to those skilled in the art; for example, an alkaline substance can be added into the mixture.
- the alkaline substance can be a common choice in the art; for example, it can be selected from one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
- the alkaline substance can be used in a form of solid or water solution. If the alkaline substance is used in the form of water solution, the concentration can be 10 wt. % to saturated concentration.
- the initiator can be one or more selected from the group consisting of azo initiators, peroxide initiators, and redox initiators, particularly preferably a redox initiator.
- the oxidizer can be potassium persulfate and/or ammonium persulfate
- the reducer can be one or more selected from the group consisting of sodium bisulfite, sodium pyrosulfite, sodium sulfite, and sodium thiosulfate.
- the dosage of the initiator can be 0.1-0.9 parts by weight, preferably 0.3-0.6 parts by weight.
- the weight ratio of oxidizer to reducer can be 0.5-1.5:1, most preferably 1:1.
- the polymerization reaction conditions include reaction temperature is 30-60° C., reaction time is 15-60 min., and pH is 6-9.
- cross-linking reaction conditions there is no specific restriction to the cross-linking reaction conditions in the present invention, as long as at least a part of the structural units expressed by formula (2) can be bonded with at least a part of the structural units expressed by formula (3) into the cross-linked structural units expressed by formula (4); for example, the cross-linking reaction conditions include reaction temperature is 90-100° C. and reaction time is 2-6 h.
- the cross-linking reaction is preferably carried out in an enclosed environment.
- the apparent viscosity of the product of the olefinic polymerization and the apparent viscosity of the filtrate reducer for drilling fluid there is no specific restriction to the apparent viscosity of the product of the olefinic polymerization and the apparent viscosity of the filtrate reducer for drilling fluid; preferably, the apparent viscosity of 1 wt. % water solution of the product obtained from olefinic polymerization is 5-7.5 mPa ⁇ s, and the apparent viscosity of 1 wt. % water solution of the filtrate reducer for drilling fluid is 30-55 mPa ⁇ s.
- the apparent viscosity is measured with a Fan-35 rotary viscometer at 25° C.
- the increased apparent viscosity of the polymer solution proves the occurrence of the cross-linking reaction.
- the method for preparation of the filtrate reducer for drilling fluid further comprises a process of shearing, drying, and crushing the obtained product of cross-linking reaction in step (II).
- the shearing, drying, and crushing procedures are known to those skilled in the art, and will not be detailed further here.
- the present invention provides the use of the acryloylmorpholine polymer as a filtrate reducer for drilling fluid.
- the apparent viscosity of 1 wt. % water solution of the product obtained from the olefinic polymerization reaction and the apparent viscosity of the 1 wt. % water solution of acryloylmorpholine polymer are measured with a Fan-35 rotary viscosimeter at 25° C.
- the contents of the structural units in the acryloylmorpholine polymer are calculated on the basis of the dosages of the monomers.
- AMPS-AA copolymer viscosity reducer produced by Zhongyuan Oilfield Drilling Engineering Technology Research Institute, coded as XJ-1, industrial product; sulfonated lignite: produced by Oilfield Chemical Co., Ltd. of Dagang Oilfield, coded as SMC, industrial product; sodium bentonite and calcium bentonite: produced by Weifang Haoda Bentonite Co., Ltd., industrial products; barite: produced by Guizhou Kali Longteng Mining Co., Ltd., with 4.32 g/cm 3 density.
- the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 9.17 mol
- the total content of the structural units expressed by formula (3) and cross-linked structural units expressed by formula (4) is 0.047 mol
- the apparent viscosity of 1 wt. % water solution of the gelatinous elastic cross-linked polymer is 55 mPa ⁇ s.
- the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 2.17 mol
- the total content of the structural units expressed by formula (3) and cross-linked structural units expressed by formula (4) is 0.016 mol
- the apparent viscosity of 1 wt. % water solution of the gelatinous elastic cross-linked polymer is 45 mPa ⁇ s.
- the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 1.32 mol
- the total content of the structural units expressed by formula (3) and cross-linked structural units expressed by formula (4) is 0.013 mol
- the apparent viscosity of 1 wt. % water solution of the gelatinous elastic cross-linked polymer is 42.5 mPa ⁇ s.
- the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 0.70 mol
- the total content of the structural units expressed by formula (3) and cross-linked structural units expressed by formula (4) is 0.011 mol
- the apparent viscosity of 1 wt. % water solution of the gelatinous elastic cross-linked polymer is 33.5 mPa ⁇ s.
- Example 5 6 7 8 50% (mass percent) water solution of SAMPS/g 180 180 180 180 N-acryloylmorpholine/g 25.5 42 60 79 Water/mL 5 30 40 70 Initiator ammonium persulfate/g 0.3 0.35 0.4 0.45 sodium sulfite/g 0.3 0.35 0.4 0.45 Cross-linked N-methylol acrylamide/g — — — 0.6 monomer hydroxy-ethyl acrylate/g — — 0.5 — hydroxy-ethyl methacrylate/g 0.25 — — — hydroxy-propyl acrylate/g — 0.40 — pH 7 9 8 8 Static reaction temperature/time (° C./min.) 30/30 30/20 30/40 30/60 Constant temperature reaction temperature/time (° C./h) 100/3 95/4 100/6 90/2.5 Apparent viscosity of 1 wt.
- the 2-acrylamide sodium hexanesulfonate monomer used in this Example (with the structure expressed by formula (2), wherein, R 4 -R 7 are H, y is 5, and M is Na) is prepared with the following method: add 371 g acrylonitrile into a 500 mL reaction bulb with agitator, thermometer, dropping funnel, and vent tube, decrease the temperature to 0° C. with ice water bath, and add 104 g fuming sulfuric acid in droplets within 45 min at 0-10° C. Then, decrease the temperature to ⁇ 10° C., add 84 g 1-hexene in droplets within 90 min at 20° C., and keep the reaction for 60 min at 35° C.
- the total content of the structural units expressed by formula (2) and cross-linked structural units expressed by formula (4) is 2.14 mol
- the total content of the structural units expressed by formula (3) and cross-linked structural units expressed by formula (4) is 0.018 mol
- the apparent viscosity of 1 wt. % water solution of the gelatinous elastic cross-linked polymer is 41.5 mPa ⁇ s.
- the apparent viscosity of 1 wt. % water solution of the reference filtrate reducer for drilling fluid is 36.0 mPa ⁇ s.
- the apparent viscosity of 1 wt. % water solution of the viscous product is 4.25 mPa ⁇ s.
- Control the obtained viscous product to have constant temperature reaction for 2 h at 100° C.; shear, dry, and crush the product, to obtain a reference filtrate reducer for drilling fluid, wherein, the apparent viscosity of 1 wt. % water solution of the reference filtrate reducer for drilling fluid is 4.5 mPa ⁇ s.
- Test Examples 1-9 are provided here to describe the evaluation of the performance of the acryloylmorpholine polymer and filtrate reducer for drilling fluid provided in the present invention.
- the base mud and testing method used in the evaluation are:
- Compound brine base mud add 45 g NaCl, 5 g anhydrous CaCl 2 , 13 g MgCl 2 .6H 2 O, 150 g calcium bentonite, and 9 g anhydrous Na 2 CO 3 into 1,000 mL distilled water, agitate at a high speed (at 10,000 rpm agitation speed, the same below) for 20 min., and maintain for 24 h at 25° C., to obtain a compound brine base mud.
- High calcium-content brine base mud 5 wt. % sodium bentonite+40 wt. % CaCl 2 +2.5 wt. % anhydrous Na 2 CO 3 +5.0 wt. % sulfonated lignite+1.0 wt. % AMPS-AA copolymer viscosity reducer+46.5 wt. % water, weight up with barite to 1.5 g/cm 3 density, agitate at a high speed for 20 min, and maintain for 24 h at 25° C., to obtain a high calcium-content brine base mud.
- Saturated brine base mud 6 wt. % sodium bentonite+36 wt. % NaCl+2.5 wt. % anhydrous Na 2 CO 3 +2 wt. % sulfonated lignite+53.5 wt. % water, weight up with barite to 1.5 g/cm 3 density, agitate at a high speed for 20 min, and maintain for 24 h at 25° C., to obtain a saturated brine base mud.
- AV ⁇ 600 2
- ⁇ 600 is the reading obtained with the six-speed rotary viscosimeter at 600 r/min rotation speed.
- the dosages of the filtrate reducers for drilling fluid and the results are shown in Table 2.
- Comparative Test Examples 1-2 are provided here to describe the evaluation of the performance of the reference filtrate reducers for drilling fluid.
- the acryloylmorpholine polymer filtrate reducer for drilling fluid achieves outstanding filtrate reduction and viscosity increasing effects after aging for 16 h at 220° C., which is far better than the effects that can be achieved with the polymers obtained in the Comparative Examples after aging for 16 h at 220° C., which is to say, the filtrate reducer for drilling fluid provided in the present invention has outstanding temperature tolerance and salt resistance performance, and is very suitable for use in well drilling application in ultra deep wells, high pressure and high saline-content formations.
Abstract
Description
wherein, R1-R9 are H or C1-C3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R10 is C1-C5 linear or branched alkylidene.
wherein, R1-R9 are H or C1-C3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R10 is C1-C5 linear or branched alkylidene.
wherein, R1-R9 are H or C1-C3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R10 is C1-C5 linear or branched alkylidene.
wherein, R1-R9 are H or C1-C3 linear or branched alkyl respectively, y is an integer within 1-5, M is H or an alkali metal element, X is O or NH, and R10 is C1-C5 linear or branched alkylidene.
TABLE 1 | ||
Example |
5 | 6 | 7 | 8 | ||
50% (mass percent) water solution of SAMPS/g | 180 | 180 | 180 | 180 |
N-acryloylmorpholine/g | 25.5 | 42 | 60 | 79 |
Water/mL | 5 | 30 | 40 | 70 |
Initiator | ammonium persulfate/g | 0.3 | 0.35 | 0.4 | 0.45 |
sodium sulfite/g | 0.3 | 0.35 | 0.4 | 0.45 | |
Cross-linked | N-methylol acrylamide/g | — | — | — | 0.6 |
monomer | hydroxy-ethyl acrylate/g | — | — | 0.5 | — |
hydroxy-ethyl methacrylate/g | 0.25 | — | — | — | |
hydroxy-propyl acrylate/g | — | 0.40 | — | — |
pH | 7 | 9 | 8 | 8 |
Static reaction temperature/time (° C./min.) | 30/30 | 30/20 | 30/40 | 30/60 |
Constant temperature reaction temperature/time (° C./h) | 100/3 | 95/4 | 100/6 | 90/2.5 |
Apparent viscosity of 1 wt. % water solution of the viscous | 6.25 | 6.5 | 5.5 | 6 |
product (mPa · s) | ||||
Apparent viscosity of 1 wt. % water solution of the gelatinous | 43.5 | 44.5 | 37.5 | 39.5 |
elastic cross-linked polymer (mPa · s) |
Content of | Structural units expressed by formula (1) | 1 | 1 | 1 | 1 |
structural units | Structural units expressed by formula (2) + | 2.17 | 1.32 | 0.92 | 0.70 |
(mol) | structural units expressed by formula (4) | ||||
Structural units expressed by formula (3) + | 0.011 | 0.010 | 0.010 | 0.011 | |
structural units expressed by formula (4) | |||||
wherein, Φ600 is the reading obtained with the six-speed rotary viscosimeter at 600 r/min rotation speed. The dosages of the filtrate reducers for drilling fluid and the results are shown in Table 2.
PV=Φ600−Φ300
wherein, Φ600 is the reading obtained with the six-speed rotary viscosimeter at 600 r/min rotation speed, and Φ300 is the reading obtained with the six-speed rotary viscosimeter at 300 r/min rotation speed. The dosages of the filtrate reducers for drilling fluid and the results are shown in Table 2.
YP=0.48(Φ300−PV)
wherein, Φ300 is the reading obtained with the six-speed rotary viscosimeter at 300 r/min rotation speed, and PV is plastic viscosity. The dosages of the filtrate reducers for drilling fluid and the results are shown in Table 2.
TABLE 2 | ||||
Base mud and | Comparative | |||
dosage of | Properties of | Base | Example | Example |
filtrate reducer | drilling fluid | mud | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 |
Compound | Apparent | 3.5 | 11.5 | 13.5 | 12.0 | 11.5 | 13.0 | 12.5 | 11.5 | 13.5 | 13.0 | 5.0 | 7.5 |
brine base mud, | viscosity/mPa · s | ||||||||||||
dosage of | Plastic viscosity/ | 3 | 9 | 10 | 9 | 8.5 | 10 | 9 | 9 | 9.5 | 10.5 | 4.0 | 6.0 |
filtrate reducer | mPa · s | ||||||||||||
is 2.5 wt. % | Yield point/Pa | 0.5 | 2.5 | 3.5 | 3.0 | 3.0 | 3.0 | 3.5 | 2.5 | 4.0 | 2.5 | 1.0 | 1.5 |
Filter loss/mL | 162 | 12.0 | 11.0 | 12.5 | 9.0 | 14.0 | 12.3 | 11.0 | 11.5 | 11.2 | 78 | 32 | |
High | Apparent | 3.5 | 13.5 | 10.5 | 15.5 | 12.5 | 10.5 | 14.5 | 14.0 | 11.0 | 14.0 | 8.0 | 9.0 |
calcium-content | viscosity/mPa · s | ||||||||||||
brine base mud, | Plastic viscosity/ | 3 | 7 | 5 | 10 | 7.5 | 6 | 9 | 8 | 5.5 | 8 | 6 | 6 |
dosage of | mPa · s | ||||||||||||
filtrate reducer | Yield point/Pa | 0.5 | 6.2 | 5.5 | 5.5 | 5.0 | 4.5 | 5.5 | 6.0 | 5.5 | 6 | 2 | 3 |
is 3.5 wt. % | Filter loss/mL | 168 | 13.5 | 12.4 | 13.0 | 13.4 | 15.5 | 12.0 | 13.8 | 14.5 | 13.1 | 195 | 65 |
Saturated brine | Apparent | 12 | 28 | 31 | 35 | 30 | 30.5 | 33 | 32 | 33 | 29 | 18 | 22 |
base mud, | viscosity/mPa · s | ||||||||||||
dosage of | Plastic viscosity/ | 9 | 23 | 25 | 28 | 26 | 26 | 27 | 27 | 27 | 23 | 13 | 17 |
filtrate reducer | mPa · s | ||||||||||||
is 3.5 wt. % | Yield point/Pa | 3 | 5 | 6 | 7 | 4 | 4.5 | 6 | 5 | 6 | 6 | 5 | 5 |
Filter loss/mL | 230 | 17 | 19.5 | 18 | 22 | 20.4 | 19.0 | 18.3 | 19.8 | 18.5 | 58 | 44 | |
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CN201310282326.3A CN103665261A (en) | 2012-09-20 | 2013-07-05 | Acryloylmorpholine polymer and application thereof as well as drilling fluid filtrate loss reducer |
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CN104388063B (en) * | 2014-10-31 | 2020-04-24 | 中国石油化工集团公司 | Micro-crosslinked polymer fluid loss additive for drilling fluid and preparation method thereof |
CN106519136B (en) * | 2015-09-10 | 2020-01-14 | 中石化石油工程技术服务有限公司 | Inverse emulsion polymer, preparation method thereof and application thereof in preparation of water-based drilling fluid |
CN106520107A (en) * | 2016-11-07 | 2017-03-22 | 重庆科技学院 | Acryloyl morpholine polymer oil-displacing agent and preparation method thereof |
CN107880214B (en) * | 2017-11-24 | 2019-10-25 | 中国海洋石油集团有限公司 | A kind of preparation method of water-soluble anionic polymer type heavy crude thinner |
CN110317304B (en) * | 2019-07-22 | 2022-06-07 | 山西庆达中安建材有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
CN112592444B (en) * | 2020-12-15 | 2022-07-12 | 山东瑞博龙化工科技股份有限公司 | Temperature-sensitive water-soluble block polymer heavy oil viscosity reducer and preparation method and application thereof |
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CN114957325B (en) * | 2021-10-29 | 2024-03-26 | 西南石油大学 | Phosphonate compound and application thereof in preparation of filtrate reducer |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20080114123A1 (en) * | 2006-10-31 | 2008-05-15 | Tighe Brian J | Polymeric compositions comprising at least one volume excluding polymer |
CN102382245A (en) | 2011-08-11 | 2012-03-21 | 中国海洋石油总公司 | High temperature-resistant polymer filtrate reducer for drilling fluid and preparation method thereof |
CN102516455A (en) | 2011-12-15 | 2012-06-27 | 东营市诺尔化工有限责任公司 | Multi-polymerization preparation method of flocculant |
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US5988279A (en) * | 1997-11-05 | 1999-11-23 | Fritz Industries, Inc. | Method for control of fluid loss and gas migration in well cementing |
US6107256A (en) * | 1998-08-27 | 2000-08-22 | Fritz Industries, Inc. | Method of and additive for controlling fluid loss from a drilling fluid |
US6124245A (en) * | 1998-10-07 | 2000-09-26 | Phillips Petroleum Company | Drilling fluid additive and process therewith |
US20050034864A1 (en) * | 2003-06-27 | 2005-02-17 | Caveny William J. | Cement compositions with improved fluid loss characteristics and methods of cementing in surface and subterranean applications |
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